Method of preparing 2-aryl-1,3-cyclohexanedione compounds

ABSTRACT

2-Aryl-1,3-cyclohexanedione compounds and their alkali metal and ammonium salts exhibit outstanding herbicidal, miticidal and mite ovicidal activity.

This application is a division of our prior U.S. application Ser. No.781,985, filing date Mar. 28, 1977, now U.S. Pat. No. 4,209,532.

This invention relates to 2-aryl-1,3-cyclohexanedione compounds andmethods of preparing same. In another aspect this invention is directedto miticidal, mite ovicidal, post-emergent herbicidal and pre-emergentherbicidal compositions comprising an acceptable carrier and apesticidally effective amount of a compound of this invention, as wellas, to methods of controlling mites and plant pests which comprisessubjecting the mites, the eggs of mites and the plant pest to apesticidally effective amount of a compound of this invention.

More particularly, this invention relates to compounds of the formula:##STR1## and alkali metal and ammonium salts thereof, wherein:

Z, Z', Z", Z'" are individually hydrogen, polyhaloalkyl, halogen, cyano,alkoxy, alkyl, nitro, alkylsulfonyl, alkylsulfinyl, alkylthio,haloalkyl, alkanoyl, amino or amido;

R₁ is alkyl, halogen, haloalkyl or polyhaloalkyl substituent;

R₂, R₃, R₄, R₅, R₆ and R₇ are individually hydrogen or eithersubstituted or unsubstituted alkyl or phenyl wherein the permissiblesubstituents are one or more alkyl, cyano, halogen, nitro, alkoxy,alkylthio, alkylsulfinyl, alkylsulfonyl, or dialkylamino substituents orany two R₂, R₃, R₄, R₅, R₆ or R₇ substituents together may form analkylene or alkenylene chain having from 2 to 20 carbon atoms completinga 3, 4, 5, 6 or 7 membered ring structure;

with the proviso that R₁, R₂, R₃, R₄, R₅, R₆, R₇ Z, Z' Z" and Z'"individually may not include more than ten aliphatic carbon atoms.

The following miticidally, mite ovicidally, mite ovicidally andherbicidally active compounds are illustrative of compounds within thepurview of the generic formula set forth above, all of which can beconveniently prepared by the processes of this invention simply byselecting appropriate reactants for use in the procedures describedbelow:

2-(2',4',6'-Trimethylphenyl)-1,3-cyclohexanedione

2-(2'-Cyano-4',6'-dichlorophenyl)-1,3-cyclohexanedione

2-(2'-Isopropyl-6'-cyanophenyl)-4,6-dimethyl-1,3-cyclohexanedione

2-(2'-Trifluoromethyl-6'-methyl)-4-trichloromethyl-1,3-cyclohexanedione

Trimethylammonium salt of2-(2',4'-dimethylphenyl)-5,5-dimethyl-1,3-cyclohexanedione

Pyrrolidinium salt of2-(2',4'-dichlorophenyl)-5,5-dimethyl-1,3-cyclohexanedione

Piperidinium salt of2-(2',5'-dimethylphenyl)-5,5-dimethyl-1,3-cyclohexanedione

1-Adamantanammonium salt of2-(2'-chlorophenyl)-5,5-dimethyl-1,3-cyclohexanedione

Pyridinium salt of 2-(2'-methylphenyl)-5,5-dimethyl-1,3-cyclohexanedione

Morpholinium salt of2-(2',4'dichlorophenyl)-5,5-dimethyl-1,3-cyclohexanedione

Benzyldimethylammonium salt of2-(2',4'-dimethylphenyl)-5,5-dimethyl-1,3-cyclohexanedione

Dicyclohexylammonium salt of2-(2'-chlorophenyl)-5,5-dimethyl-1,3-cyclohexanedione

N,N-diethylanilinium salt of2-(2',4'-dimethylphenyl)-5,5-dimethyl-1,3-cyclohexanedione

2- Picolinium salt of2-(2',4'-dichlorophenyl)-5,5-dimethyl-1,3-cyclohexanedione

Piperazinium salt of2-(2',5'-dimethylphenyl)-5,5-dimethyl-1,3-cyclohexanedione

Imidazolinium salt of2-(2'-chlorophenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2',4'-dimethylphenyl)-5-methyl-5-ethyl-1,3-cyclohexanedione

2-(2',4'-dichlorophenyl)-5,5-diethyl-1,3-cyclohexanedione

2-(2'-methyl-4'-methoxyphenyl)-5-methyl-5-isobutyl-1,3-cyclohexanedione

2-(2'-methyl-4'-chlorophenyl)-5-methyl-5-isopropyl-1,3-cyclohexanedione

2-(2'-Ethyl-6'-ethoxyphenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2',6'-Diethylphenyl)-5,5-ditrifluoromethyl-1,3-cyclohexanedione

2-(2'-Methyl-6'-(methylsulfinyl)phenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2'-Trichloromethyl-6'-cyanophenyl)-5,6-dimethyl-1,3-cyclohexanedione

2-(2',6'-Dimethyl-4'-t-butylphenyl)-5,5-dimethyl-1,3-cyclohexanedione

3-(2',4',6'-Triethylphenyl)-spiro-[5,5]undecane-2,4-dione

Trimethylammonium salt of2-(2'-ethyl-6'-ethoxy)-5,5-dimethyl-1,3-cyclohexanedione

3-(2'-Methylphenyl)-spiro[5.5]undecane-2,4-dione

5-Phenyl-2-(2',4',6'-trimethylphenyl)-1,3-cyclohexanedione

2-(2'-Methyl-4',6'-dichlorophenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2'-Nitro-4',6'-Dibromophenyl)-5,5-dimethyl-1,3-cyclohexanedione

5-(4'-Chlorophenyl0-2-(2',4',6'-trimethylphenyl)-1,3-cyclohexanedione

5-(3'-Bromophenyl)-2-(2',4',6'-trimethylphenyl)-1,3-cyclohexanedione

5-(2'-Methylthiophenyl)-2-(2',4',6'-trichlorophenyl)-1,3-cyclohexanedione

5-(4'-Methoxyphenyl)-2-(2',4',6'-trimethylphenyl)-1,3-cyclohexanedione

5-(3'-β-methoxyethylphenyl)-2-(2',4',6'-trimethylphenyl)-1,3-cyclohexanedione

2-(2',4',6'-Trimethylphenyl)-4-(4'-methylphenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2',4',6'-Trimethylphenyl)-4-phenyl-5,5-dimethyl-1,3-cyclohexanedione

2-(2',4',6'-Trimethylphenyl)-4-(4'-chlorophenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2',4',6'-Trimethylphenyl)-4-methoxy-5,5-dimethyl-1,3-cyclohexanedione

2-(2',4',6'-Trimethylphenyl)-4,5-dimethyl-1,3-cyclohexanedione

2-(2',4',6'-Trimethylphenyl)-4-(4'-dimethylaminophenyl)-5-methyl-1,3-cyclohexanedione

5-(4'-Dimethylaminophenyl)-2-(2',6'-dimethylphenyl)-4-methyl-1,3-cyclohexanedione

2-(2'-N-methylcarbamoyl-6'-methylphenyl)-4-(4'-methoxyphenyl)-5,6-dimethyl-1,3-cyclohexanedione

2-(2',6'-Dimethylphenyl)-4-(4'-methylthiophenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2'-Methyl-3',6'-dicyanophenyl)-6-(methylthioethyl)-1,3-cyclohexanedione

5-(4'-Methylsulfinylphenyl)-4,6-dimethyl-2-(2',6'-Dimethylphenyl)-1,3-cyclohexanedione

N-Methylpiperdinium salt of5-(2'-Methoxyphenyl)-2-(2',4',6'-trimethylphenyl)-1,3-cyclohexanedione

Trimethylammonium salt of2-(2',6'-Dimethylphenyl)-4-(4'-methylthiophenyl)-5,6-dimethyl-1,3-cyclohexanedione

2-(2'-Chloro-4'-methoxyphenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2'-Methyl-4'-cyanophenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2'-Methyl-4'-trifluoromethylphenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2'-Trifluoromethyl-4'-methoxyphenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2'-Trifluoromethyl-4'-chlorophenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2'-Trifluoromethyl-4'-cyanophenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2',4'-Dimethylphenyl)-5-phenyl-1,3-cyclohexanedione

2-(2'-Methylphenyl)-5-(2'-methylsulfonylmethyl)-1,3-cyclohexanedione

2-(2'-Methylphenyl)-5-(2'-chlorophenyl)-1,3-cyclohexanedione

2-(2'-Methylphenyl)-5-(4'-nitrophenyl)-1,3 cyclohexanedione

2-(2'-Methylphenyl)-5-(4'-cyanophenyl)-1,3-cyclohexanedione

2-(2',4'-Dimethylphenyl)-5-(2'-methylphenyl)-1,3-cyclohexanedione

2-(2',4'-Dimethylphenyl)-4-(4'-trifluoromethylphenyl)-1,3-cyclohexanedione

2-(2',4'-Dimethylphenyl)-5-(2'-chlorophenyl)-1,3-cyclohexanedione

2-(2',4'-Dichlorophenyl)-6-(2'-methylthiophenyl)-1,3-cyclohexanedione

3-(2',4'-Dichlorophenyl)-5-(4'-methylphenyl)-1,3-cyclohexanedione

2-(2',4'-Dichlorophenyl)-5-(4'-methoxyphenyl)-1,3-cyclohexanedione

3-(2'-Methylphenyl)-spiro[5.5]undecane-2,4-dione

3-(2',4'-Dimethylphenyl)-spiro[5.5]undecane-2,4-dione

3-(2'-Chlorophenyl)-spiro[5.5]undecane-2,4-dione

3-(2',4'-Dichlorophenyl)-spiro[5.5]undecane-2,4-dione

2-(2',4'-Dimethylphenyl)-4,5-diethyl-1,3-cyclohexanedione

2-(2',4'-Difluorophenyl)-6-methyl-1,3-cyclohexanedione

2-(2'-methyl-5'-cyanophenyl)-6-methoxymethyl-1,3-cyclohexanedione

2-(2',4'-Dibromophenyl)-4-(4'-methylthiophenyl)-5-methyl-1,3-cyclohexanedione

2-(2',4'-Dichlorophenyl)-6-(4'-dimethylaminophenyl)-1,3-cyclohexanedione

2-(2'-Trifluoromethyl-5-cyanophenyl)-6-methylsulfinylethyl-1,3-cyclohexanedione

2-(2'-chloro-4'-methoxyphenyl)-4,6-dimethyl-1,3-cyclohexanedione

The pyridinium salt of2-(2',4'-Dibromophenyl)-6-methoxymethyl-1,3-cyclohexanedione

The N-methylmorpholinium salt of2-(2'-methylphenyl)-4,6-diethyl-1,3-cyclohexanedione

5-(2',4'-Dimethylphenyl)-2-(2',4',6'-trichlorophenyl)-1,3-cyclohexanedione

5-(2',4'-Dichlorobutyl)-2-(2'-ethoxy-3',5',6'-trifluorophenyl)-1,3-cyclohexanedione

5-(Methylthiomethyl)-2-(2'-chloro-6'-cyanophenyl)-1,3-cyclohexanedione

5-(2'-Dimethylaminophenyl)-2-(2',6'-dimethylphenyl)-1,3-cyclohexanedione

2-(2'-Nitro-3'-methylthio-6'-trichloromethylphenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2'-methyl-5'-cyano-6'-nitrophenyl)-4,6-dimethyl-1,3-cyclohexanedione

2-(2',4'-Dichloro-6'-trifluoromethylphenyl)-4-(2'-chloroethyl)-1,3-cyclohexanedione

3-(2'-Chloro-6'-fluorophenyl)-spiro[5.5]undecane-2,4-dione

2-(2'-Chloro-4'-nitro-6'-cyanophenyl)-5,5-propyl-1,3-cyclohexanedione

2-(2',6'-Dichloro-4'-nitrophenyl)-5-(2'-cyanoethyl)-1,3-cyclohexanedione

2-(2'-Chloro-6'-methoxy-4'-nitrophenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2'-Chloro-6'-cyano-4'-nitrophenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2'-Bromo-6'-methoxyphenyl)-1,3-cyclohexanedione

2-(2'-Methyl-6'-nitrophenyl)-1,3-cyclohexanedione

2-(2'-Trifluoromethyl-6'-nitrophenyl)-1,3-cyclohexanedione

2-(2',6'-Dichloro-4'-nitrophenyl)-1,3-cyclohexanedione

2-(2'-Chloro-6'-methoxy-4'-nitrophenyl)-1,3-cyclohexanedione

2-(2'-Chloro-6'-cyano-4'-nitrophenyl)-1,3-cyclohexanedione

2-(2'-Chloro-4',6'-dinitrophenyl)-1,3-cyclohexanedione

2-(2'-Methyl-4',6'-dinitrophenyl)-1,3-cyclohexanedione

4-(4'-Chlorophenyl)-2,(2'-chloro-4'-nitrophenyl)-1,3-cyclohexanedione

5-(4'-Cyanophenyl)-2-(2'-chloro-6'-methoxy-4'-nitrophenyl)-1,3-cyclohexanedione

5-(2',4'-Dichlorophenyl)-2-(2',4'-dichloro-6'-nitrophenyl)-1,3-cyclohexanedione

5-(3'-Nitrophenyl)-2-(2'-chloro-4'-nitrophenyl)-1,3-cyclohexanedione

5-Phenyl-2-(2'-methyl-6'-chloro-4'-nitrophenyl)-1,3-cyclohexanedione

3-(2'-Chloro-6-nitrophenyl)-spiro[5.5]undecane-2,4-dione

3-(2',6'-Dichloro-4'-nitrophenyl)-spiro[5.5]undecane-2,4-dione

2-(2'-Trifluoromethyl-4'-aminophenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2', 4'-Dichloro-6'-aminophenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2',6'-Dichloro-4'-aminophenyl)-5,6-dimethyl-1,3-cyclohexanedione

2-(2'-Chloro-6'-nitro-4'-aminophenyl)-5,5-dimethyl-1,3-cyclohexanedione

5-(4'-Chlorophenyl)-2-(2'-chloro-6'-methoxy-4'-aminophenyl)-1,3-cyclohexanedione

5-(4'-Chloro-6'-nitrophenyl)-2-(2'-bromo-4'-methylsulfinyl-6'-cyanophenyl)-1,3-cyclohexanedione

3-(2'-Chloro-6'-aminophenyl)-spiro[5.5]undecane-2,4-dione

2-(2',6'-Dichloro-4'-aminophenyl)-1,3-cyclohexanedione

2-(2'-Methyl-6'-nitrophenyl)-5-methoxymethyl-1,3-cyclohexanedione

2-(2'-Chloro-6'-nitrophenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2'-Methyl-6'-nitrophenyl)-1,3-cyclohexanedione

2-(2'-Chloro-6'-nitrophenyl)-1,3-cyclohexanedione

2-(2'-Chloro-6'-methoxyphenyl)-5,6-dimethyl-1,3-cyclohexanedione

2-(2'-Chloro-6'-methoxyphenyl)-4,4-dimethyl-1,3-cyclohexanedione

2-(2'-Methyl-3'-nitro-6'-methoxyphenyl)-4,5-dimethyl-1,3-cyclohexanedione

2-(2'-Chloro-6'-methoxyphenyl)-1,3-cyclohexanedione

2-(2'-Methyl-4'-nitro-6'-methoxyphenyl)-1,3-cyclohexanedione

2-(2'-Bromo-4'-nitro-6'-idophenyl)-4,5-dimethyl-1,3-cyclohexanedione

2-(2'-Bromo-4'-aminophenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2',6'-Dibromophenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2'-Bromo-6'-aminophenyl)-1,3-cyclohexanedione

2-(2'-Bromo-5'-chloro-6'-fluorophenyl)-1,3-cyclohexanedione

2-(2',4'-Dichlorophenyl)-5,5-dimethyl-1,3 cyclohexanedione

2-(2'4-Dichloro-6'-tribromomethylphenyl)-1,3-cyclohexanedione

2-(2',4',6'-Trifluorophenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2',4',6'-Tribromophenyl)-1,3-cyclohexanedione

3-(2'-Chloro-6'-bromophenyl)-spiro[5.5]undecane-2,4-dione

3-(2',4',6'-Trimethylphenyl)-spiro[5.5]undecane-2,4-dione

3-(2',4',6'-Trichlorophenyl)-spiro[5.5]undecane-2,4-dione

2-(2'-Methyl-6'-cyano-5'-nitrophenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2'-Methyl-6'-cyano-4'-nitrophenyl)-1,3-cyclohexanedione

2-(2'-Chloro-6'-cyanophenyl)-1,3-cyclohexanedione

2-(2'-Chloro-4'-cyanophenyl)-6-trichloromethyl-1,3-cyclohexanedione

2-(2',6'-Dichloro-4'-cyanophenyl)-1,3-cyclohexanedione

5-(2',4'-Dimethoxyphenyl)-2-(2',6'-dimethylphenyl)-1,3-cyclohexanedione

5-(2'-Cyanopropyl)-6-methyl-2-(2',6'-dimethylphenyl)-1,3-cyclohexanedione

5-(3'-Ethylsulfinylphenyl)-2-(2',6'-dichlorophenyl)-1,3-cyclohexanedione

3-(2',4'-Dimethylphenyl)-bicyclo[3.2.1]octane-2,4-dione

3-(2',4'-Dichlorophenyl)-bicyclo[4.4.0]decane-2,4-dione

All compounds within the purview of the above generic formula exhibitmiticidal, mite ovicidal, preemergent herbicidal and post-emergentherbicidal activity to a lesser or greater extent. Some of thesecompounds exhibit very high levels of miticidal, mite ovicidal orherbicidal activity in extremely small dosages while others requirelarger dosages to be pesticidally effective. In general, the compoundsof this invention that exhibit the highest order of herbicidal activityalso exhibit the highest order of miticidal and mite ovicidal activity.Miticidal and mite ovicidal activity is greatest in those compoundshaving a hydrogen, alkyl, alkoxy, cyano, trihalomethyl or halogensubstituent at one of the ortho positions of the 2-phenyl moiety and analkyl or halogen substituent at the other ortho position of the 2-phenylmoiety. Especially active compounds are those in which the orthosubstituents are relatively small groups such as methoxy, ethoxy,methyl, ethyl, or halogen.

It has also been found that some of the pesticidal compositions of thisinvention exhibit excellent fumigant properties. In addition, thesecompounds are relatively non-toxic to mammals when used in amountssufficient to kill mites, mite eggs or plant pests.

In addition to their utility as miticides, mite ovicides and herbicides,the compounds of this invention are also useful as intermediates in thepreparation of other pesticidally active compounds. For example,2-(2'-chloro-6'-methoxy-4'-nitrophenyl)-5,5-dimethyl-1,3-cyclohexanedionecan be reacted with 2-ethylhexanoyl chloride in the presence of pyridineas solvent and acid acceptor to form3-(2-ethylhexanoyloxy)-2-(2'-chloro-6'-methoxy-4'-nitrophenyl)-5,5-dimethyl-2-cyclohexenone,the corresponding pesticidally active enol ester compound. The2-aryl-1,3-cyclohexanedione compounds of this invention can also bereacted with other chemical species containing electron deficientreaction sites as for example organic anhydride compounds such as aceticanhydride. Certain reactions leading to the pesticidally active enolester derivatives are described in more detail in my copending UnitedStates Patent Application Ser. No. 781,781 entitled "Biocidal2aryl-1,3-cyclohexanedione Enol Ester Compounds", filed Mar. 28, 1977.

Preferred because of their higher levels of miticidal, mite ovicidal andherbicidal activity and because of their utility as intermediates in thepreparation of other pesticidally active compounds are the compounds ofthis invention in which,

Z, Z' and Z" are individually alkyl, hydrogen, cyano, alkoxy, halogen ortrihalomethyl;

R₁ is alkyl, or halogen;

R₂, R₃, R₄, R₅, R₆ and R₇ are individually hydrogen or alkyl.

The most active and particularly preferred compounds are those in which,

Z, Z', Z" and Z'" are individually hydrogen, methyl, methoxy, cyano orhalogen;

R₁ is methyl or halogen;

R₂, R₃, R₄, R₅, R₆ and R₇ are individually hydrogen, methyl or ethyl;

The 2-aryl-1,3-cyclohexanedione compounds of this invention can beconveniently prepared by a variety of methods. Two preferred methods forpreparing the compounds of this invention are illustrated by thereaction schemes set below in which R₁, R₂, R₃, R₄, R₅, R₆, R₇, Z, Z',Z" and Z'" are as described above and R₈ is alkyl except as noted:##STR2##

Preferably, the reactions illustrated in Methods I and II are carriedout by contacting equivalent amounts of the reactants in a suitablesolvent. In the conduct of the reaction of Method II, types andquantities of the solvent employed are not critical. Illustrative ofsuitable inert solvents are ethanol, methanol, dimethylformamide,dimethylsulfoxide, methylene chloride, benzene, xylene, toluene,dioxane, dimethoxyethane, tetrahydrofuran and the like.

The reaction illustrated in METHOD I can be conducted in any solventthat is chemically inert to the reactants and to the reactionconditions, and in which the acid catalyst is soluble. Illustrative ofsuch solvents are water and carboxylic acids, such as acetic acid,butanoic acid, or the like. The preferred reaction solvents are waterand acetic acid.

The cyclization reaction illustrated in Method I is conducted in thepresence of a strong mineral acid catalyst. Illustrative of mineralacids that are useful in the conduct of this reaction are sulfuric acid,hydrochloric acid, perchloric acid and the like. The preferred acidcatalyst is sulfuric acid.

The quantity of acid catalyst employed in the conduct of the reaction ofMethod I is not critical. In general, to achieve a reasonable rate ofreaction, the reaction is conducted in the presence of from about 1 toabout 85 weight percent of the acid catalyst based on the total weightof the reaction solvent. Preferred acid concentrations are from about 50to about 85 weight percent based on the weight of the reaction solvent.

The cyclization reaction illustrated in Method II is conducted in thepresence of at least one equivalent of either a strong organic or astrong inorganic base. Illustrative of bases that are useful in theconduct of this reaction are the alkali metal alkoxides, as for example,sodium methoxide, sodium ethoxide or potassium tert-butoxide; the alkalimetal alkylides; or the alkali metal hydrides such as sodium hydride,lithium hydride or the like. The preferred base in the conduct of thisreaction is sodium hydride.

The reaction pressure and temperature at which the reaction of Method'sI and II are conducted are not critical. For convenience, thesereactions are usually conducted at atmospheric or autogeneous pressure.In general, these reactions can be conducted at a temperature in therange of from about -30° C. and upwards to approximately 200° C. andhigher. Preferred reaction temperatures are from about 60° to about 120°C.

Alternative procedures for preparing a more limited class of2-aryl-1,3-cyclohexanedione compounds are illustrated by the generalreaction schemes set forth below in which R₁, R₂, R₃, R₄, R₅, R₆, R₇, Z,Z', Z" and Z'" are as described above and X is fluorine or chlorine,except as noted: ##STR3## In Method III, R₁ is alkyl and Z, Z', Z" andZ'" are other than nitro. ##STR4## In Method IV, Z' is alkylsulfonyl ornitro; or Z' may also be alkyl or alkoxy when either R₁ or Z'" is nitro.

The procedure illustrated in METHOD III involves the photosensitizeddecomposition of a 2-diazocycloalkane-1,3-dione compound in an aromaticsolvent, in the presence of a photosensitizer, preferably benzophenone.In this procedure an appropriately substituted2-diazocycloalkane-1,3-dione compound is photochemically decomposed toform the corresponding triplet carbene which, in turn, reacts with asuitable aromatic solvent to form the desired2-arylcycloalkane-1,3-dione compound. The photolysis reaction is carriedout using ultraviolet radiation having a wavelength of greater than 290nanometers. The ultraviolet radiation can be obtained from anyconventional ultraviolet radiation source known to those skilled in thephotolysis art. Illustrative of suitable sources for generatingultraviolet radiation are high and low pressure mercury arc lamps,germacidal lamps, "black" lights and the like.

Preferably the reaction illustrated in METHOD IV is carried out bycontacting equivalent amounts of the reactants in an appropriatesolvent, in the presence of at least an equivalent of either an organicor an inorganic base. Illustrative of suitable reaction solvents, aredimethylformamide, dimethylsulfoxide, hexamethylphosphoramide and thelike. Illustrative of bases that may be utilized in the conduct of thisreaction are alkali metal carbonates or bicarbonates, as for example,sodium bicarbonate or potassium carbonate; alkali metal hydrides, suchas lithium hydride, sodium hydride or potassium hydride, or alkali metalalkoxides or hydroxides, such as sodium hydroxide, sodium methoxide orpotassium tert-butoxide. The preferred base is anhydrous potassiumcarbonate.

The reactions of Methods III and IV are neither temperature nor pressuresensitive and may be conducted over a braod temperature and pressurerange to yield the desired product. In general, these reactions can beconducted at a temperature of from about -30° C. to about 200° C. Forconvenience these reactions are conducted at autogeneous or atmosphericpressure.

The alkali metal and ammonium salts of the compounds of this inventioncan be conveniently prepared in accordance with conventional methods.For example, the alkali metal and ammonium salts can be prepared bytreating the corresponding 2-aryl-1,3-cyclohexanedione compound with analkali metal alkoxide, or ammonia, or an amine respectively.

The 6-aryl-5-ketopolyalkylhexanoic acid compounds utilized as reactantsin the reaction illustrated in Method I can be conveniently prepared byreacting an appropriately polysubstituted benzyl cyanide compound with asuitable polyalkyl glutaric acid derivative in the presence of base toform the corresponding 6-aryl-6-cyano-5-ketopolyalkylhexanoic acid estercompound which, in turn, is hydrolyzed under acidic conditions to thedesired reactant.

The 6-aryl-5-ketopolyalkylhexanoic acid ester compounds utilized asreactants in the reaction illustrated in Method II can be convenientlyprepared by esterifying the 6-aryl-5-ketopolyalkylhexanoic acid reactantof Method I via conventional esterification techniques.

The 2-diazo-1,3-cyclohexanedione compounds utilized as reactants in thereaction of Method III can be prepared by treating an appropriatelysubstituted cyclohexanedione-1,3-dione compound with a sulfonyl azide inthe presence of an acid acceptor, as for example, a trialkylamine, asdescribed in more detail in H. Stetter and K. Kiehr, Chem. Ber., 98 1181(1965), M. Regitz and P. Stodler, Liebigs Ann. Chem., 687, 214 (1967)and references cited therein. The cyclohexane-1,3-dione compound, inturn, can be prepared by conventional methods, as for example bycondensing an appropriately substituted α-β-unsaturated ketone withdiethyl malonate in the presence of a base catalyst as described in moredetail in K. W. Rosenmund, H. Hertzberg and H. Scutt, Chem. Ber., 87,1258 (1954), C. K. Shuang and Y. L. Tien, Chem. Ber., 69, 27 (1936) andreferences cited therein.

The substituted aryl and cyclohexanedione compounds employed asreactants in the reaction illustrated in Method IV are known classes ofcompounds that can be either obtained from commercial sources orprepared in accordance with conventional methods known to those skilledin the synthetic arts.

The following specific examples are presented to more particularlyillustrate the novel process of this invention and its use in preparingthe novel compounds of this invention.

EXAMPLE I Preparation of2-(2'-Chloro-4'-nitrophenyl)-5,5-dimethyl-1,3-cyclohexanedione

A solution containing 42.05 g (0.300 mol) of5,5-dimethyl-1,3-cyclohexanedione and 100 g (0.718 g-atom) of anhydrouspotassium carbonate in 300 ml of dry dimethylformamide was heated to 75°C. under nitrogen and stirred for one hour. The3,4-dichloronitrobenzene, 57.60 g (0.300 mol) was dissolved in 100 mldimethylformamide and added dropwise to the reaction mixture whilestirring and maintaining the temperature of the reaction mixture at 75°C. A deep red-colored solution formed, and when the addition wascomplete the reaction temperature was raised to 100° C. and held at thistemperature for 3 hours. Most of the dimethylformamide was removed byvacuum distillation. The residue was poured into 21 of ice water andextracted three times with 500 ml of benzene. Nitrogen was then passedthrough the aqueous solution while warming to remove dissolved benzene.The aqueous solution was cooled in an ice bath and acidified to give atacky precipitate, which, upon warming solidified and was collected bysuction filtration. The product was recrystallized from acetone to give31.7 g (36%) of2-(2'-Chloro-4'-nitrophenyl)-5,5-dimethyl-1,3-cyclohexanedione as awhite powder, m.p. 250°-253° C.

Calculated for C₁₄ H₁₄ ClNO₄.1/2H₂ O: C, 55.18; H, 4.96; N, 4.60. Found:C, 55.53; H, 4.73; N, 5.09.

EXAMPLE II Preparation of2-(2'-Chloro-4'-aminophenyl)-5,5-dimethyl-1,3-cyclohexanedione

A solution of 20.0 g (0.067 mol) of2-(2'-chloro-4'-nitrophenyl)-5,5-dimethyl-1,3-cyclohexanedione in 150 mlof concentrated ammonium hydroxide and 150 ml of ethanol was stirred atroom temperature while passing hydrogen sulfide gas through the solutionat such a rate that all of the H₂ S was absorbed. When the solution wassaturated with H₂ S, the temperature was raised to the reflux point andH₂ S continuously passed slowly through the refluxing solution for 24hours. The reaction mixture was filtered to remove sulfur, and thefiltrate evaporated under reduced pressure. To the residue was added 300ml of 0.25 N NaOH, and the solution filtered once more. The filtrate wascooled and carefully acidified to pH=4 with 6 N HCl.2-(2'-Chloro-4'-aminophenyl)-5,5-dimethyl-1,3-cyclohexanedione wascollected by suction filtration.

Yield: 13.3 g (74%), m.p. 218°-219° C. Calculated for: C₁₄ H₁₆ClNO₂.1/2H₂ O. C, 61.20, H, 6.24; N, 5.10. Found: C, 60.44; H, 5.83; N,5.32.

EXAMPLE III Preparation of2-(2'-Chlorophenyl)-5,5-dimethyl-1,3-cyclohexanedione

2-(2'-Chloro-4'-aminophenyl)-5,5-dimethyl-1,3-cyclohexanedione (9.66 g.0.0364 mol) was added to 7.0 ml of water, and the mixture stirred andheated almost to boiling. An additional 15.0 ml of HCl was added and themixture cooled to 0°-5° C. A solution of 3.22 g (0.0467 mol) of sodiumnitrite in 9.0 ml of water was added dropwise while the reaction mixturewas stirred and maintained at 0°-5° C. When the addition of the sodiumnitrite solution was complete, the reaction mixture was stirred at 0°-5°C. for one hour.

The diazonium salt solution prepared above was added in portions to 161ml of 50% hypophosphorous acid at 0° C., with stirring and cooling. Thereaction mixture was stirred for 12 hours and filtered to give 8.55 g ofa tan solid. This material was chromatographed through 250 g of silicagel (0.063-0.2 mm) eluting with a gradient from pure benzene to 70:30benzene-ethyl acetate. A total of 7.12 g of reaction product wasobtained from the chromatography and recrystallized from benzene-ethylacetate to give 6.85 g (75%) of2-(2'-Chorophenyl)-5,5-dimethyl-1,3-cyclohexandione as white crystals,m.p. 191°-192° C.

Calculated for C₁₄ H₁₅ C₁ O₂ : C, 67.07; H, 6.03. Found: C, 67.04; H,6.00.

EXAMPLE IV Preparation of2-(2',4'-Dichlorophenyl)-5,5-dimethyl-1,3-cyclohexanedione

A fresh sample of cuprous chloride was prepared by slowly adding asolution of 2.09 g of sodium bisulfite and 1.38 g of NaOH in 20 ml ofwater to a solution of 9.86 g CuSO₄.5H₂ O and 2.75 g NaCL in 100 ml ofhot water. The suspension of CuCl was cooled to room temperature, andwashed several times with water while exercising care to avoid exposureof the cuprous chloride to air.

A suspension of 5.00 g (0.0188 mol) of2-(2'-chloro-4'-aminophenyl)-5,5-dimethyl-1,3-cyclohexanedione in 75 mlof water containing 4.0 ml of concentrated HCl was stirred and heatedalmost to boiling for 10 min., then cooled to 10° C. and an additional 7ml of conc. HCl added and the solution cooled to 0°-5° C. A solution of2.00 g (0.0282 mol) of sodium nitrite in 6.0 ml of water was addeddropwise to the amine hydrochloride solution while maintaining thetemperature at 0°-5° C. When all the NaNO₂ solution had been added, thediazonium salt solution was stirred for 30 min. at 0° C.

The diazonium salt solution was added, in small portions to a solutionof the cuprous chloride in 40 ml of conc. HCl at 0° C. When all of thediazonium salt solution had been added, the reaction mixture was stirredovernight at room temperature and filtered to give 6.22 g of a tansolid, m.p. 175°-178° C. This crude product was chromatographed throughsilica gel (0.063-0.2 mm) using a benzene-ethyl acetate gradient frompure benzene to 70:30 benzene-ethyl acetate to give 3.51 g (65%) of2-(2,4'-Dichlorophenyl-5,5-dimethyl-1,3-cyclohexanedione as a white,crystalline solid, m.p. 208.5°-210° C.

Calculated for: C₁₄ H₁₄ Cl₂ O₂ : C, 58.97; H, 4.95. Found: C, 59.06; H,4.82

EXAMPLE V Preparation of2-(2',6'-Dichloro-4'-nitrophenyl)-5,5-dimethyl-1,3-cyclohexanedione

A solution of 30.98 g (0.221 mol) of 5,5-dimethyl-1,3-cyclohexanedioneand 76.36 g (0.553 mol) of anhydrous potassium carbonate in 300 ml ofdimethylformamide was heated to 75° C. with stirring under N₂ for onehour. The 3,4,5-trichloronitrobenzene (50.0 g, 0.221 mol) was dissolvedin 100 ml of dimethylformamide and added to the reaction mixture, whilestirring and maintaining the temperature at 75° C. A deep red-coloredsolution was formed, and when the addition was complete the temperaturewas raised to 100° C. and the mixture stirred over night at thistemperature. Most of the dimethylformamide was removed by vacuumdistillation, and 21 of water was added to the residue. The aqueoussolution was extracted three times with 500 ml portions of benzene, thenN₂ was passed through the aqueous solution while warming to removedissolved benzene. The solution was cooled in an ice bath and acidifiedwith 6 N HCl to give 63.8 g(87%) of2-(2',6'-dichloro-4'-nitrophenyl)-5,5-dimethyl-1,3-cyclohexanedione as atan powder, m.p. 288°-290° C.

Calculated for C₁₄ H₁₃ Cl₂ NO₄ : C, 50.93; H, 3.97; N, 4.24. Found: C,50.09; H, 3.79; N, 4.26

EXAMPLE VI Preparation of2-(2',6'-Dichloro-4'-aminophenyl)-5,5-dimethyl-1,3-cyclohexanedione

A solution of 20.0 g (0.0606 mol) of2-(2',6'-dichloro-4'-nitrophenyl)-5,5-dimethyl-1,3-cyclohexanedione in150 ml conc. NH₄ OH and 150 ml of ethanol was stirred at roomtemperature while passing H₂ S gas through the solution at such a ratethat all of the H₂ S was absorbed. After the solution was saturated withH₂ S, it was refluxed 24 hours while continuously passing H₂ S slowlythrough the solution. The reaction mixture was cooled to roomtemperature, the precipitated sulfur removed by filtration, and thefiltrate evaporated to dryness under reduced pressure. To the residuewas added 300 ml of 0.25 N NaOH, and the solution filtered once more.The filtrate was cooled and acidified to pH-4 with 6 N HCl. A tan solidformed which was collected by filtration to give 11.2 g when dry. Thismaterial was washed with methylene chloride to give 8.2 g (45%) of2-(2',6'-dichloro-4'-aminophenyl)-5,5-dimethyl-1,3-cyclohexanedione as awhite powder, m.p. 243° d.

Calculated for C₁₄ H₁₅ C₁₂ NO₂ : C, 56.02; H, 5.04; N, 4.67. Found: C,56.34; H, 4.95; N, 4.67.

EXAMPLE VII Preparation of2-(2',6'-Dichlorophenyl)-5,5-dimethyl-1,3-cyclohexane dione

The 2-(2',6'-dichloro-4'-aminophenyl)-5,5-dimethyl-1,3-cyclohexanedione(5.00 g, 0.0167 mol) was added to 3.5 ml of concentrated HCl in 75 ml ofwater, and the mixture stirred and heated almost to boiling. Thesuspension was cooled to 10° C. and an additional 7.5 ml of conc. HClwas added. The mixture was cooled to 0°-5° C. and a solution of 1.44 g(0.0209 mol) of sodium nitrite in 3.5 ml. of water was added dropwisewhile the reaction mixture was stirred and maintained at 0°-5° C. Whenaddition of the sodium nitrite solution was complete, the reactionmixture was stirred at 0° C. for one hour.

The diazonium salt solution prepared above was added in portions to 75ml of 50% hypophosphorous acid at 0° C. with stirring and cooling. Thereaction mixture was stirred for 2 hours filtered to give 5.03 g ofbrown powder. This material was recrystallized from benzene-chloroformto give 2.69 g of a light tan solid m.p. 227°-229° C. The residue fromthe mother liquor (1.70 g) was chromatographed through silica gel(0.063-0.2 mm) to give 0.84 g of a white solid, m.p. 228°-232° C. Totalyield of 2-(2',6'-Dichlorophenyl)-5,5-dimethyl-1,3-cyclohexane-1,3-dionewas 3.53 g (74%).

Calculated for: C₁₄ H₁₄ Cl₂ O₂ : C, 58.97; H, 4.95. Found: C, 58.64; H,4.86

EXAMPLE VIII Preparation of2-(2',4',6'-Trimethylphenyl)-cyclohexane-1,3-dione

A solution of 5.00 g (0.036 mol) of 2-diazocyclohexane-1,3-dione in 500ml of mesitylene (dry, distilled) containing 32.8 g (0.18 mol)benzophenone was degassed with nitrogen for one hour and irradiated witha 200 watt mercury arc lamp fitted with a borosilicate glass filteruntil the complete disappearance of the diazo band (4.68 u) in theinfrared was observed. The reaction was also monitored by thin layerchromatography (90:10 ethyl acetate-benzene) and irradiation continueduntil no diazoketone at R_(f) =0.31 could be seen. The irradiationrequired 11 hours. The mesitylene was extracted with 0.25 N sodiumhydroxide until a small aliquot showed no cloudiness upon acidification.The combined base extracts were washed twice with 200 ml portions ofether, and acidified (pH 3-5) with 1 N HCl. The aqueous solution wasextracted three times with 75 ml portions of chloroform, dried overanhydrous MgSO₄, and the solvent stripped to give 5.06 g of a tan solid.

This solid was chromatographed through 250 g silica gel (0.063-0.2 mm)eluting with a gradient from pure benzene to 80:20 benzene-ethylacetate. A total of 2.60 g (31%) of a white solid (homogeneous by thinlayer chromatography) was obtained and recrystallized from diisopropylether to give 1.96 g of2-(2',4',6'-Trimethylphenyl)-cyclohexane-1,3-dione as white crystals, mp196°-198° C.

Calculated for: C₁₅ H₁₈ O₂ : C, 78.23; H, 7.88. Found: C, 77.94; H, 8.20

EXAMPLES IX and X Preparation of2-(2',4'-Dimethylphenyl)-5,5-dimethylcyclohexane-1,3-dione and2-(2',6'-dimethylphenyl)-5,5-dimethylcyclohexane-1,3-dione

A solution of 5.00 g (0.0301 mol.) of2-diazo-5,5-dimethylcyclohexane-1,3-dione in 500 ml of m-xylenecontaining 27.4 g (0.15 mol) of benzophenone was degassed with nitrogenfor one hour and irradiated overnight with a 200 watt mercury arc lampfitted with a borosilicate glass filter. The photolysis mixture wasextracted with 0.25 N NaOH, the combined base extracts washed with etherand acidified with chloroform, dried over anhydrous mgSO₄ and thesolvent removed to leave 3.61 g of a tan solid. Irradiation was repeatedusing 7.00 g (0.042 mol) of 2-diazo-5,5-dimethylcyclohexane-1,3-dioneand 38.38 g (0.21 mol) of benzophenone in 500 ml of m-xylene. Workupgave 5.48 g of tan solid.

The combined crude products (9.09 g) were chromatographed through silicagel (0.063-0.2 mm) using benzene-ethyl acetate as eluent. The column waseluted with (1) 500 ml benzene (2) 500 ml of 95.5 benzene-ethyl acetate(3) 1000 ml of 90:10 benzene-ethyl acetate and (4) 1000 ml of 80:20benzene-ethyl acetate. After collecting 2 liters of solvent, the columnwas attached to an automatic fraction collector and 15 ml fractionscollected. Tubes 1-94 contained small amounts of a yellow oil. Tubes95-150 contained a light yellow solid which showed one component (R_(f)0.55 in 50:50 hexane-ethyl acetate) by thin layer chromatography andweighted 2.18 g. This material was recrystallized from benzene to give1.17 g of 2-(2',4'-Dimethylphenyl)-5,5-dimethyl-1,3-cyclohexanedione asa white powder, mp 167°-169° C.

Calculated for: C₁₆ H₂₀ O₂ : C, 78.65; H, 8.25. Found: C, 78.68; H, 8.12

This compound was shown to be2-(2',4'-dimethylphenyl)-5,5-dimethyl-1,3-cyclohexanedione.

Tubes 151-230 were combined to give 2.0 g of white solid showing onecomponent (R_(f) 0.57 in 50:50 hexane-ethyl acetate by thin layerchromatography. This material was recrystallized from benzene to give1.90 g of 2-(2',6'-Dimethylphenyl)-5,5-dimethyl-1,3-cyclohexanedione aswhite crystals, mp 177°-186° C.

Calculated for: C₁₆ H₂₀ O₂ : C, 78.65; H, 8.25. Found: C, 78.28; H, 8.21

This compound was shown to be2-(2',6'-Dimethylphenyl)-5,5-dimethyl-1,3-cyclohexanedione.

EXAMPLE XI Preparation of 2-Diazo-5-phenylcyclohexane-1,3-dione

A solution of 20.0 g (0.106 mol) of 5-phenylcyclohexane-1,3-dione in 75ml ethanol was cooled to -10° C. and stirred magnetically undernitrogen. To the mixture was added 10.75 g (0.106 mol) of triethylamine.The tosyl azide (20.95 g 0.106 mol) was added all at once, and themixture stirred for one hour at 0°-5° C. The solvent was removed undervacuum at a temperature less than 40° C. To the residue was added 200 mlether, and the mixture extracted with a solution containing 3.1 gpotassium hydroxide in 200 ml of water. The ethereal solution was driedover anhydrous MgSO₄ filtered and the solvent removed to give a yellowsolid which was recrystallized from ethanol-hexane to give 8.38 g (32%)of 2-diazo-5-phenylcyclohexane-1,3-dione as yellow crystals, mp122°-124° C.

EXAMPLE XII Preparation of2-(2',4',6'-Trimethylphenyl)-5-phenylcyclohexane- 1,3-dione

A solution of 7.0 g (0.0327 mol) of2-diazo-5-phenylcyclohexane-1,3-dione and 29.77 g (0.163 mol) ofbenzophenone in 500 ml of mesitylene was degassed for one hour withnitrogen and irradiated with a 200 watt mercury arc lamp fitted with aborosilicate glass filter overnight. The photolysis mixture wasextracted with 0.25 N sodium hydroxide, the combined base extractswashed with ether, acidified with 1 N HCl, and extracted withchloroform. The chloroform solution was dried over anhydrous MgSO₄, andthe solvent stripped to give 5.7 g of tan solid. This material waspurified by column chromatography on silica gel (0.063-0.2 mm) usingbenzene-ethyl acetate to give 5.7 g (57%) of a white solid. This wasrecrystallized from benzene-ethyl acetate to give 4.08 g (41%) of2-(2',4',6'-Trimethylphenyl)-5-phenylcyclohexane-1,3-dione as a whitecrystalline solid, mp. 215°-216° C.

Calculated for: C₂₁ H₂₂ O₂ : C, 82.32; H, 7.24. Found: C, 82.38; H, 7.14

EXAMPLE XIII Preparation of2-(2',6'-Dimethyl-4'-t-butylphenyl)-5,5-dimethyl-1,3-cyclohexanedione

A solution of 7.00 g (0.042 mol) of2-diazo-5,5-dimethylcyclohexane-1,3-dione in 300 ml of5-t-butyl-m-xylene and 250 ml chlorobenzene containing 38.38 g (0.21mol) of benzophenone was irradiated overnight with a 200 watt mercuryarc lamp fitted with a borosilicate glass filter after degassing for 1hour under nitrogen. The photolysis mixture was extracted with 0.25 NNaOH, washed with ether, acidified with 1 N HCl, and extracted withchloroform. The chloroform was dried over anhydrous MgSO₄ and strippedto give a crude yellow solid. The photolysis was repeated and thecombined crude product from these reactions was chromatographed throughsilica gel (0.063-0.2 mm) using benzene-ethyl acetate. The solidobtained from the chromatography was recrystallized from benzene to give2.76 g (11%) of2-(2',6'-dimethyl-4'-t-butylphenyl)-5,5-dimethyl-13-cyclohexanedione aswhite crystals, mp 244°-49° C.

Calculated for: C₂₀ H₂₈ O₂ : C, 79.95; H, 9.39. Found: C, 79.76; H, 9.45

EXAMPLE XIV Preparation of 2-Diazodecalin-1,3-dione

A solution of 10.0 g (0.0768 mol) of decalin-1,3-dione in 50 ml ofethanol was magnetically stirred under nitrogen and cooled to -10° C. Tothe solution was added 7.77 g (0.0768 mol) of triethylamine followed by15.14 g (0.0768 mol) of p-toluenesulfonylazide added all at once. Themixture was stirred for one hour at 0° C., and the solvent removed atreduced pressure at a temperature of less than 40° C. To the residue wasadded 200 ml of ether, and the ether removed to yield a yellow solid.This was recrystallized from ethanol to give 5.23 g of yellow crystals,mp 81°-83° C.

EXAMPLE XV Preparation of 2-(2'-Methylphenyl)-decalin-1,3-dione

A solution of 7.0 g (0.0364 mol) of 2-diazodecalin-1,3-dione and 33.18 g(0.182 mol) of benzophenone in 500 ml of toluene was degassed for onehour with nitrogen and irradiated with a 200 watt mercury arc lampfitted with a borosilicate glass filter overnight. The photolysismixture was extracted with 0.25 N NaOH, the combined base extractswashed with ether, acidified with 1 M HCl and extracted with chloroform.The chloroform extracts were dried over anhydrous MgSO₄, and the solventremoved to give 4.56 g of a yellow crude product. This was purified bycolumn chromatography through silica gel (0.063-0.2 mm) withbenzeneethyl acetate. The solid obtained was recrystallized from benzeneto give 1.85 g (20%) of 2-(2'-Methylphenyl)-decalin-1,3-dione as whitecrystals, mp 165°-167° C.

Calculated for: C₁₇ H₂₀ O₂ : C, 79.65; H, 7.86. Found: C, 79.82; H, 7.43

EXAMPLE XVI Preparation of Ethyl6-(2',4'-Dimethylphenyl)-6-cyano-5-keto-3,3-dimethylhexanoate

A clean, dry 500 ml 3-neck flask was equipped with a reflux condenser,mechanical stirrer, addition funnel and nitrogen inlet. The flask wascharged with 70 ml of absolute ethanol followed by 6.00 g (0.26 g-atom)of sodium, and the reaction mixture stirred and heated until all thesodium had dissolved. The temperature of the reaction mixture was thenraised to the reflux point, and a mixture of 29.04 g (0.20 mol) of2,4-dimethylbenzyl cyanide and 64.88 g (0.30 mol) of diethyl3,3-dimethyl glutarate added, dropwise, over a 2 hour period through theaddition funnel. When the addition was complete, the reaction mixturewas maintained at reflux for 12 hrs. At the end of this time,approximately 2/3 of the ethanol was distilled off, and the reactionmixture refluxed for 2 hrs. more, then cooled to room temperature andpoured into 600 ml of an ice water mixture.

The basic aqueous solution was extracted twice with 300 ml of ether, andthen acidified (pH=3) with 6 N HCl. An oil formed, and the aqueous acidsolution was extracted twice with 250 ml portions of ether. The etherphase from the extraction of the aqueous acid was washed twice withwater, dried over anhydrous MgSO₄, and stripped to leave 52.83 g (84%)of ethyl 6-(2',4'-Dimethylphenyl)-6-cyano-5-keto-3,3-dimethylhexanoateas a clear, colorless, very viscous oil. This oil was not purified, butwas characterized by infrared and nuclear magnetic resonancespectrometry.

IR (neat, μ, principal absorptions): 2.8-3.2 (OH, enol); 4.55 (C.tbd.N);5.85, 6.02, 6.19 (C═O); 6.3 (C.tbd.C); 7.45, 8,25, 9.85, 12.25.

NMR (CDCl₃,δ): 1.20 (multiplet, 9H); 2.33 (multiplet, 8H); 2.68(multiplet, 2H); 4.17 (quartet, 2H): 4.90 and 12.0 (singlet, 1H); 7.05(multiplet, 3H).

EXAMPLE XVII Preparation of2-(2',4'-Dimethylphenyl)-5,5-dimethyl-1,3-cyclohexanedione and6-(2',4'-Dimethylphenyl)-5-keto-3,3-dimethylhexanoic acid

A one-neck round bottom flask was charged with 52.50 g (0.17 mol) ofethyl 6-(2',4'-dimethylphenyl)-6-cyano-3,3-dimethylhexanoate, 250 ml ofconcentrated hydrochloric acid, 250 ml of glacial acetic acid, and 100ml of water. The reaction mixture was stirred and refluxed for 48 hours.After 12 hours and 24 hrs. of refluxing, an additional 100 ml of conc.HCl and 100 ml glacial HOAC were added. After 48 hours, the mixture wasstripped to dryness under reduced pressure. To the residue were added150 ml of water and 150 ml of ethyl ether, and the mixture shakenvigorously. A white, crystalline precipitate formed, and this wasremoved by suction filtration to give 13.20 g (32%) of2-(2',4'-Dimethylphenyl)-5,5-dimethyl-1,3-cyclohexanedione as a white,crystalline solid, m.p. 167°-168.5° C.

Calcd. for C₁₆ H₂₀ O₂ : C, 78.65; H, 8.25. Found: C, 78.68; H, 8.12

The ether layer was separated from the filtrate, washed once with water,dried over anhydrous MgSO₄ and stripped to give 29.04 g (65%) of6-(2',4'-dimethylphenyl)-5-keto-3,3-dimethylhexanoic acid as a viscousyellow oil. This oil was not purified, but was characterized by infraredand nuclear magnetic resonance spectrometry.

IR (CHCl₃, μ, principal absorptions): 2.9-4.3 (OH); 5.90 (C.tbd.O).

NMR (CDCl₃,δ): 1.10 (singlet, 6H); 2.20 singlet, 3H); 2.30 (singlet,3H); 2.50 (singlet, 2H); 2.62 (singlet, 2H); 3.70 (singlet, 2H); 7.08(singlet, broad, 3H).

EXAMPLE XVIII Preparation of 2-(2'-Chlorophenyl)-1,3-cyclohexanedione

A 500 ml round bottom flask was charged with 10.0 g (0.0416 mol) of6-(2'-chlorophenyl)-5-ketohexanoic acid and 100 ml of 72% sulfuric acid.The reaction mixture was stirred and heated to 120° C. for 51/2 hours(oil bath), then poured into 600 ml of an ice water mixture. A tacky,white solid formed, and this was extracted into 300 ml of methylenechloride. The CH₂ Cl₂ solution was washed six times with water, driedover anhydrous MgSO₄ and stripped to leave 8.87 g of a tacky, whitesolid. This material was recrystallized from ethyl acetate to give 5.85g (63%) of 2-(2'-chlorophenyl)-1,3-cyclohexanedione as a white,crystalline solid, m.p. 148.5°-149° C.

Calculated for: C₁₂ H₁₁ ClO₂ : C, 64.73; H, 4.98. Found: C, 64.49; H,4.89

EXAMPLE XIX Preparation of 6-(2',4'-Dimethylphenyl)-5-ketohexanoic acid

Utilizing the procedure of EXAMPLE XVII ethyl6-(2',4'-dimethylphenyl)-6-cyano-5-ketohexanoate was hydrolyzed in thepresence of concentrated hydrochloric acid to prepare6-(2',4'-dimethylphenyl)-5-ketohexanoic acid in 49% yield as a tansolid, m.p. 75.0°-76.5° C. This solid was characterized by infrared andnuclear magnetic resonance spectrometry.

IR (CHCl₃, μ, principal absorptions): 2.9-4.2 (OH); 5.92 (C═O).

NMR (CDCl₃,δ): 1.7-3.3 (multiplet, 6H); 2.48 (singlet, 3H); 3.71(singlet, 2H); 7.31 (singlet, broad, 3H).

EXAMPLE XX Preparation of Ethyl 6-(2',4'-Dimethylphenyl)-5-ketohexanoate

A 500 ml one-neck round bottom flask equipped with a Soxhlet extractionapparatus containing 100 g of molecular sieves having a pore size of 3 Awas charged with 12.74 g (0.0544 mol) of6-(2',4'-dimethylphenyl)-5-ketohexanoic acid, 125 ml of absoluteethanol, 125 ml of dry benzene, and 2.0 ml of concentrated sulfuricacid. The mixture was refluxed for 12 hours, then 2/3 of theethanolbenzene removed under reduced pressure. The residue was pouredinto 500 ml of ice water, and extracted into 300 ml of ether. The etherwas washed three times with 10% K₂ CO₃, then once with water, dried overanhydrous MgSO₄, and removed to leave 13.34 g of a dark yellow oil. Thiswas distilled to give 12.77 g (89%) of ethyl6-(2',4'-Dimethylphenyl)-5-ketohexanoate as a clear, colorless oil, b.p.133°-145° C. (0.05 mm). This oil was further characterized by infraredand nuclear magnetic resonance spectrometry.

IR (neat, μ, principal absorptions): 5.85 (C═O), 8.60 (C═O).

NMR (CDCl₃,δ): 1.15 (triplet, 3H); 1.50-2.6 (multiplet, 6H); 2.10(singlet, 3H); 2.20 (singlet, 3H; 3.52 (singlet, 2H); 3.95 (quartet,2H); 6.80 (singlet, broad, 3H).

EXAMPLE XXI Preparation of 2-(2',4'-Dimethylphenyl)-1,3-cyclohexanedione

A 500 ml 3-neck round bottom flask was equipped with a mechanicalstirrer, addition funnel, and reflux condenser. The glassware was driedthoroughly and the flask charged with 4.62 g (0.096 g-atoms) of 50%sodium hydride in mineral oil. The oil was washed off the NaH usingtoluene, and then 100 ml of toluene added. The mixture was warmed to 65°C. and 12.62 g (0.0481 mol) of ethyl6-(2',4'-dimethylphenyl)-5-ketohexanoate added, dropwise, over a 2 hr.period. The mixture was maintained at 65° C. for 12 hrs., then carefullyquenched with 25 ml of ice water. The reaction mixture was diluted with250 ml of water and extracted twice with 150 ml of ether. The aqueousbase solution was acidified to pH=3 with 6 N HCl, and extracted twicewith 150 ml of methylene chloride. The methylene chloride was washedwith water, dried over anhydrous MgSO₄, and stripped to give 5.88 g of asemisolid. This was recrystallized from ethyl acetate to give 5.10 g(49%) of 2-(2',4'-Dimethylphenyl)-1,3-cyclohexanedione as a white,crystalline solid, m.p. 143°-145° C.

Calculated for: C₁₄ H₁₆ O₂ : C, 77.75; H, 7.46. Found: C, 76.99; H, 7.46

EXAMPLE XXII Preparation of Ethyl6-(2',5'-Dimethylphenyl)-6-cyano-5-keto-3,3-dimethylhexanoate

Utilizing the procedure of EXAMPLE XVI, 29.04 g (0.200 mol) of2,5-dimethylbenzyl cyanide and 64.88 g (0.300 mol) of diethyl3,3-dimethyl glutarate were reacted to yield 45.24 g (72%) of ethyl6-(2',5'-dimelhylphenyl)-6-cyano-5-keto-3,3-dimethylhexanoate as aclear, colorless viscous oil. Structure was confirmed by infrared andnuclear magnetic resonance spectrometry.

IR (neat, μ, principal absorptions): 2.9-3.7 (OH, enol); 4.55 (C═N);5.80, 5.98, 6.10 (C═O); 6.23 (C═C); 7.35; 7.60; 8.15; 9.70; 12.30.

MNR (CDCl₃,δ): 1.18 (multiplet, 9H); 1.67-2.73 (multiplet, 10H); 4.12(quartet, 2H); 4.88 (singlet 1H); 7.05 (broad, singlet, 3H).

EXAMPLE XXIII Preparation of6-(2',5'-Dimethylphenyl)-5-keto-3,3-dimethylhexanoic acid and2-(2',5'-Dimethylphenyl-5,5-dimethyl-1,3-cyclohexanedione

A solution of 45.24 g (0.14 mol) of ethyl6-(2',5'-Dimethylphenyl)-6-cyano-5-keto-3,3-dimethylhexanoate, 250 ml ofglacial acetic acid. 250 ml of concentrated HCl, and 70 ml of water wasrefluxed for 48 hours. After 24 hours, an additional 100 ml ofconcentrated HCl and 150 ml of glacial acetic acid were added.

After 48 hours of refluxing, the reaction mixture was cooled to roomtemperature and the solvent removed under reduced pressure. The residuewas shaken vigorously with 250 ml of water and 250 ml of diisopropylether. A white, crystalline precipitate formed which was removed bysuction filtration to give 7.90 g (23% yield) of2-(2',5'-dimethylphenyl)-5,5-dimethyl-1,3-cyclohexanedione m.p.168°-170° C.

Calculated for C₁₆ H₂₀ O₂ : C, 78.65; H, 8.25. Found: C, 78.16; H, 8.03

The ether layer was separated from the filtrate, washed once with water,dried over anhydrous MgSO₄, and stripped to give 17.97 g of6-(2',5'-Dimethylphenyl)-5-keto-3,3-dimethyl hexanoic acid as a yellowoil. This oil was not purified, but was characterized by infrared andnuclear magnetic resonance spectrometry.

IR (neat, μ, principal absorptions): 2.9-3.8 (OH); 5.90 (C═O); 12.3(aromatic).

NMR (CDCl₃,δ): 1.08 (singlet, 6H); 2.03 (singlet, 2H); 2.13 (singlet,2H); 2.27 (singlet, 3H); 2.33 (singlet, 3H); 7.0 (singlet, 3H).

EXAMPLE XXIV Preparation of Ethyl6-(2',5'-dimethylphenyl)-5-keto-3,3-dimethylhexanoate

Utilizing the procedure of Example XX6-(2',5'-dimethylphenyl)-5-keto-3,3-dimethyl hexanoic acid wasesterified with absolute ethanol in the presence of a catalytic amountof concentrated sulfuric acid to provide 15.52 g (78% yield) of ethyl6-(2',5'-dimethylphenyl)-5-keto-3,3-dimethylhexanoate as a pale viscousoil.

EXAMPLE XXV Preparation of2-(2',5'-Dimethylphenyl)-5,5-dimethyl-1,3-cyclohexanedione

Utilizing the procedure of EXAMPLE XXI,6-(2',5'-dimethylphenyl-5-keto-3,3-dimethylhexanoate was treated withsodium hydride to yield 9.87 of crude product, which onrecrystallization yielded 8.77 g (64%) of2-(2',5'-dimethylphenyl)-5,5-dimethyl-1,3-cyclohexanedione as a white,crystalline solid m.p. 167°-168° C.

Selected 2-aryl-1,3-cyclohexanedione compounds, representative of thoseuseful in accordance with this invention were tested with respect totheir miticidal, mite ovicidal and pre-emergent and post-emergentherbicidal activity.

Suspensions of the test compounds were prepared by dissolving one gramof compound in 50 milliliters of acetone in which had been dissolved 0.1gram (10 percent of the weight of compound) of an alkylphenoxy-ethanolsurfactant, as an emulsifying or dispersing agent. The resultingsolution was mixed into 160 milliliters of water to give roughly 200milliliters of a suspension containing the compound in finely dividedform. The thus prepared stock suspension contained 0.5 percent by weightof compound. The test concentrations employed in the tests describedhereinbelow were obtained by diluting the stock suspension with water.The test procedures were as follows:

MITE FOLIAGE SPRAY TEST

Adults and nymphal stages of the two-spotted mite (tetranychus urticae(Koch)), reared on Tendergreen bean plants at 80°±5° F. and 50±5 percentrelative humidity, were the test organisms. Infested leaves from a stockculture were placed on the primary leaves of two bean plants six toeight inches in height, growing in a two-and-a-half inch clay pot.150-200 Mites, a sufficient number for testing, transferred from theexcised leaves to the fresh plants in a period of twenty-four hours.Following the twenty-four hour transfer period, the excised leaves wereremoved from the infested plants. The test compounds were formulated bydiluting the stock suspension with water to provide suspensionscontaining the desired amount of test compound per million parts offinal formulation. The potted plants (one pot per compound) were placedon a revolving turntable and sprayed with 100-110 milliliters of testcompound formulation by use of a DeVilbis spray gun set at 40 psi. airpressure. This application, which lasted 30 seconds, was sufficient towet the plants to run-off. As a control, 100-110 milliliters of a watersolution containing acetone and emulsifier in the same concentrations asthe test compound formulation, but containing no test compound, werealso sprayed on infested plants. The sprayed plants were held at 80°±5°F. and 50±5 percent relative humidity for four days, after which, amortality count of motile forms was made on the leaves of the testplants. Any individual which was capable of locomotion upon prodding wasconsidered living.

MITE OVICIDE TEST

The test organism was the egg of the two-spotted mite (Tetranychusurticae (Koch)), as obtained from adults reared on Tendergreen beanplants under controlled conditions of 80°±5° F. and 50±5 percentrelative humidity. Heavily infested leaves from a stock culture wereplaced on the primary leaves of two bean plants six to eight inches inheight, growing in a two-and-a-half inch clay pot. Females were allowedto oviposit for a period of 48 hours and then the leaves of the infestedplants were dipped in a solution containing 800 parts of tetraethylpyrophosphate per million parts of water in order to destroy thereproductory forms and thus prevent further egg laying. This solution oftetraethyl pyrophosphate does not affect the viability of the eggs. Theplants were allowed to dry thoroughly. The test compounds wereformulated by diluting the stock suspension with water to give asuspension containing varying amounts of test compound per million partsof final formulation. The potted plants (one pot per compound) wereplaced on a revolving turntable and sprayed with 100-110 milliliters oftest compound formulation by use of a DeVilbis spray gun set at 40 psig.air pressure. This application which lasted 30 seconds, was sufficientto wet the plants to run-off. As a control, 100-110 milliliters of awater solution containing acetone and emulsifier in the sameconcentrations as the test compound formulation, but containing no testcompound, were also sprayed on plants infested with eggs. The sprayedplants were held at 80°±5° F. and 50±5 percent relative humidity forfour days, after which a microscopic examination was made of unhatched(dead) and hatched (living) eggs.

In these tests the pesticidal activity of the compounds against mitesand mite eggs was rated as follows:

A=Excellent Control

B=Partial Control

C=No Control

PRELIMINARY HERBICIDE SEED GERMINATION TEST

The following seeds were used in this test:

    ______________________________________                                        Perennial rye grass                                                                            Solium perenne                                               Crabgrass        Digitaria sanguinalis                                        Red root pigweed Amaranthus retroflexus                                       Mustard          Brassica pincea var.                                                          foliosa (Florida broadleaf)                                  ______________________________________                                    

Two seed-oil mixtures were prepared as follows:

    ______________________________________                                        Mixture I      196 cc. Rye grass seed                                                        75 cc. Mustard seed                                                           18,000 cc. Sifted, fairly dry soil                             Mixture II     99 cc. Crabgrass seed                                                         33 cc. Amaranthus                                                             18,000 cc. Sifted, fairly dry soil                             ______________________________________                                    

Each of the above mixtures was rolled separately in 5 gallon containersfor approximately one-half hour on ball mill to insure uniform mixing ofseeds and soil. For each compound four 3-inch pots were filled with soilto within 11/2 inches of top of pots. To 2 of these pots were added 70cc. of Mixture I. To the remaining 2 pots were added 70 cc. of MixtureII. The seed-soil mixture was tamped firmly, and the pots were removedto the greenhouse and watered lightly. About 2 hours after planting, 25milliliters of the test formulation were added to each of 2 pots foreach soil-seed mixture; i.e., one replicate of each seed mixture perconcentration. An equal volume of a water solution containing acetoneand an emulsifier in the same concentration as the herbicidal mixturebut without the candidate herbicide was also added to each of thesoil-seed mixtures. These pots are used as check or control units. Thetest compounds were formulated by standard procedure of dissolving inacetone, addition of an emulsifier, and dilution with water. Tests wereconducted on all compositions at low concentration (100 ppm.). Certaincompositions were also tested at high concentration (1000 ppm). The potswere held in the greenhouse and watered lightly until results weretaken. Ten to twelve days after application of chemical, injury wasnoted for each species by comparing treated vs. untreated pots. Ratingswere made at both the high and the low concentrations (1000 ppm and 100ppm) according to the following designations:

5=no seedlings emerged

4=few seedlings emerged and/or very severe stunting

3=moderate reduction in stand and/or moderate stunting.

2=very slight reduction in stand and/or slight stunting

1=no injury; seedlings appear no different with respect to stand orgrowth than untreated controls

POST-EMERGENT HERBICIDAL TEST

Experiments were also conducted to determine the phytotoxicity ofrepresentative compositions with respect to healthy fresh plants.Solutions of the compounds were prepared as described above to provide aconcentration of 2500 parts per million of the test compound. The testplants were sprayed in accordance with the procedure described above forthe Mite Foliage Spray Test so as to deliver approximately 100milliliters of test solution to the leaves of each plant tested. Thesprayed plants and controls were set aside for approximately one hour toallow the solutions to dry and were then placed in the greenhouse. Afterten days the plants were visually inspected to determine the extent offoliage injury. A rating of 1 indicates no perceptible injury; 5indicates the plant was dead and ratings of 2, 3 and 4 indicateintermediate degrees of injury based upon the number and extent to whichleaves were injured.

The results of these experiments are summarized and set forth in Table Ibelow.

    TABLE I      PHYSICAL PROPERTIES AND BIOLOGICAL ACTIVITY OF 2-ARYL-1, 3-CYCLOHEXANEDI     ONE COMPOUNDS AND THEIR ALKALI METAL SALTS      ##STR5##       Post-Emergent Herbicidal Pre-Emergent Herbicidal  MP° Miticidal      Tom- Cot- Soy-   Crab-  Amar-  R.sub.1 Z"' R.sub.5 R.sub.6 Z' Z" Y C.     Adult Egg Bean Corn ato ton bean Rye grass anthus Mustard        ClHHH H H H 148.5- A A 2 4 1 2 2 5 5 1 2        149 Cl H H H Cl H H     163- A A 2 3 2 2 1 5 5 3 3        165 CH.sub.3 H H H H H H 146- B C 2 4     1 2 2 5 4 2 3        147 CH.sub.3 H H H CH.sub.3 H H 143.5- A A 2 3 2 2     2 5 5 1 2        145 CH.sub.3 H CH.sub.3 CH.sub.3 H H H 178- A A 1 1 1 1     1 5 5 1 3        179.5 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 H H 167- A     A 2 1 2 2 1 5 5 4 4        168.5 CH.sub.3 H CH.sub.3 CH.sub.3 H CH.sub.3     H 168- A A 2 1 2 2 1 5 5 3 3        169 Cl H CH.sub.3 CH.sub.3 CH.sub.3     Cl H 238- C B 1 1 2 1 1 5 1 1 1        240 Cl H CH.sub.3 CH.sub.3 H H     Na.sup.+ >250 A A 2 4 1 2 1 5 5 4 4 Cl H H H H H Na.sup.+ >250 A B 3 4 1     2 2 5 5 3 3 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 H Na.sup.+ >250 A A 2     5 1 2 2 5 5 3 5 Cl H CH.sub.3 CH.sub.3 Cl H Na.sup.+ >250 A A 2 4 2 2 2     5 5 5 5 CF.sub.3 H CH.sub.3 CH.sub.3 NO.sub.2 H H 235- C C 1 1 1 1 1 1 1     1 1        237 CF.sub.3 H CH.sub.3 CH.sub.3 H H H 209- B C 1 1 1 1 1 4 3     3 2        211.5 CF.sub.3 H CH.sub.3 CH.sub.3 Cl H H 209.5- A B 1 1 1 1     1 5 4 3 2        211 CH.sub.3 H CH.sub.3 CH.sub.3 NO.sub.2 H H 240- C C     1 1 1 1 1 1 1 1 2        245 CH.sub.3 NO.sub.2 CH.sub.3 CH.sub.3     NO.sub.2 H H 233- C C 1 1 1 3 2 1 1 1 1        235 CH.sub.3 NO.sub.2     CH.sub.3 CH.sub.3 H H H 226- A B 1 1 1 2 1 4 3 3 2        229 CN H     CH.sub.3 CH.sub.3 NO.sub.2 H H 234d C C 1 1 1 1 1 1 1 1 1 Cl NO.sub.2     CH.sub.3 CH.sub.3 NO.sub.2 H H 238d C C 1 1 1 1 1 1 1 1 1 Cl H CH.sub.3     CH.sub.3 NO.sub.2 H H 248- C C 2 2 2 2 3 1 1 1 1        251 Cl H     CH.sub.3 CH.sub.3 CH.sub.3 H H 141- A A 1 2 1 1 1 5 5 3 3        142 Cl     H CH.sub.3 CH.sub.3 Cl H H 207- A A 1 1 1 1 1 5 5 3 3209 Cl Cl CH.sub.3     CH.sub.3 NO.sub.2 H H 288- C C 1 1 1 1 1 1 1 1 1290 Cl Cl CH.sub.3     CH.sub.3 H H H 227- A A 1 3 2 2 1 5 5 1 3        229 CH.sub.3 CH.sub.3 H     H CH.sub.3 H H 196- A A 3 4 2 1 1 5 5 2 2        198 CH.sub.3 CH.sub.3     CH.sub.3 CH.sub.3 CH.sub.3 H H 212- A A 1 2 1 2 1 5 5 1 3        216     CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H H H 177- A A 1 1 2 1 2 5 5 1 2        186 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 H HH 118- C C 2 5 2 2 2 5 5     1 1        121                   CH.sub.3 CH.sub.3      ##STR6##      CH.sub.3 H H 196-202 C C 1 1 1 1 1 5 5 1 3 CH.sub.3 H CH.sub.3 CH.sub.3 C     l H H 190- A B 1 1 1 1 1 5 4  3 3        192 CH.sub.3 Cl CH.sub.3     CH.sub.3 H H H 188- A A 1 1 1 1 1 5 4 3 3        191 CH.sub.3 CH.sub.3 H C     .sub.6 H.sub.5 CH.sub.3 H H 215- C C 1 1 1 2 1 5 5 4 3        216     CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 C(CH.sub.3).sub.3 H H 244- C C 1 1 1     1 1 1 1 1 1249 CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 H H H 161- C C 1 3     2 2 2 5 5 1 3        164 OCH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 H H 115-     C C 2 3 2 1 2 5 5 2 2        119 CH.sub.3 OCH.sub.3 CH.sub.3 CH.sub.3 H     H H 172- A B 1 2 1 1 1 5 5 1 3        174 CH.sub.3 OCH.sub.3 CH.sub.3CH.s     ub.3 CH.sub.3 H H 155- A A 1 5 1 2 2 1 1 1 1        159        (a)     CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 OCH.sub.3 H H 155- A A 1 5 1 2 2 1 1     1 1        159                   CH.sub.3 H      ##STR7##      H H H 143-145 A A 1 1 1 1 2 5 5 2 3 CH.sub.3 H CH.sub.3 CH.sub.3 CN H H 1     88- A C 2 1 1 2 1 1 1 1 1191 CH.sub.3 CN CH.sub.3 CH.sub.3 H H H 193- A     C 2 2 2 2 1 1 1 1 1        195     (a)a mixture of the two isomers

It will be understood that the plant species employed in the above testsare merely representative of a wide variety of plant pest that can becontrolled by the use of the compounds of this invention. The compoundscontemplated in this invention may be applied as mite ovicides,miticides and pre-emergent herbicides according to methods known tothose skilled in the art. Pesticidal compositions containing thecompounds as the active toxicant will usually comprise a carrier and/ordiluent, either liquid or solid.

Suitable liquid diluents or carriers include water, petroleumdistillates, or other liquid carriers with or without surface activeagents. Liquid concentrates may be prepared by dissolving one of thesecompounds with a nonphytotoxic solvent such as acetone, xylene, ornitrobenzene and dispersing the toxicants in water with the aid ofsuitable surface active emulsifying and dispersing agents.

The choice of dispersing and emulsifying agents and the amount employedis dictated by the nature of the composition and the ability of theagent to facilitate the dispersion of the toxicant. Generally, it isdesirable to use as little of the agent as is possible, consistent withthe desired dispersion of the toxicant in the spray so that rain doesnot re-emulsify the toxicant after it is applied to the plant and washit off the plant. Nonionic, anionic, amphoteric or cationic dispersingand emulsifying agents may be employed; for example, the condensationproducts of alkylene oxides with phenol and organic acids, alkyl arylsulfonates, complex ether alcohols, quaternary ammonium compounds, andthe like.

In the preparation of wettable powder or dust or granulatedcompositions, the active ingredient is dispersed in and on anappropriately divided solid carrier such as clay, talc, bentonite,diatomaceous earth, fullers earth, and the like. In the formulation ofthe wettable powders the aforementioned dispersing agents as well aslignosulfonates can be included.

The required amount of the toxicants contemplated herein may be appliedper acre treated in from 1 to 200 gallons or more of liquid carrierand/or diluent or in from about 5 to 500 pounds of inert solid carrierand/or diluent. The concentration in the liquid concentrate will usuallyvary from about 10 to 95 percent by weight and in the solid formulationsfrom about 0.5 to about 90 percent by weight. Satisfactory sprays,dusts, or granules for general use contain from about 1/4 to 15 poundsof active toxicant per acre.

The pesticides contemplated herein prevent attack by insects and mitesupon plants or other material to which the pesticides are applied, andthey have relatively high residual toxicity. With respect to plants,they have a high margin of safety in that when used in sufficient amountto kill or repel the insects, they do not burn or injure the plant, andthey resist weathering which includes wash-off caused by rain,decomposition by ultraviolet light, oxidation, or hydrolysis in thepresence of moisture or, at least such decomposition, oxidation, andhydrolysis as would materially decrease the desirable pesticidalcharacteristic of the toxicants or impart undesirable characteristic forinstance, phytotoxicity, to the toxicants. The toxicants are sochemically inert that they are compatible with substantially any otherconstituents of the spray schedule, and they may be used in the soil,upon the seeds, or the roots of plants without injuring either the seedsor roots of plants. They may also be used in combination with otherpesticidally active compounds. When used as miticides they will normallybe applied to the foliage of the plants to be treated. When used asherbicides they may be used in the soil or directly upon the seeds to betreated. It will be appreciated that the compounds of this invention canalso be used in combination with other biologically active compounds.

What is claimed is:
 1. A method of preparing a compound of the formula:##STR8## which comprises treating a compound of the formula: ##STR9##with base, wherein: Z, Z', Z" and Z'" are individually hydrogen, nitro,polyhaloalkyl, halogen, cyano, alkyl, alkoxy, alkylthio, alkylsulfinyl,alkylsulfonyl, alkanoyl, amido, amino or haloalkyl.R₁ is alkyl, halogen,polyhaloalkyl, or haloalkyl; R₂, R₃, R₄, R₅, R₆ and R₇ are individuallyhydrogen or either substituted or unsubstituted alkyl or phenyl whereinthe permissible substituents are one or more alkyl, cyano, halogen,nitro, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or dialkylaminosubstituents or any two R₂, R₃, R₄, R₅ or R₆ substituents together mayform an alkylene or alkenylene chain having from 2 to 20 carboncompleting a 3, 4, 5, 6 or 7 membered ring structure; R₈ is alkyl; withthe proviso that R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, Z, Z', Z" and Z'"substituents individually may not include more than ten aliphaticcarbons.